Product for improved permanent waving of hair and simultaneously coloring and permanently waving hair and method therefor

ABSTRACT

By combining a fluoroscein-based dye with a mercaptan based permanent waving composition and maintaining the pH of the resulting composition between about 2.5 and 4.5, a composition is achieved which simultaneously colors and permanently waves the hair. In addition, even if no coloring or dyeing of the hair is desired, the use of a colorless or complimentary fluoroscein-based dye with the mercaptan based permanent waving composition achieves a composition which imparts a substantially improved curl configuration to the hair as well as substantially longer lasting curls. Preferably, the mercaptan based permanent waving composition employed comprises an ester of either thioglycolic acid, thiolactic acid, or the amide of 2-aminoethanethiol.

TECHNICAL FIELD

This invention relates to products for permanently waving hair and, moreparticularly, to products for permanently waving hair with substantiallyimproved curl retention and, if desired simultaneously coloring thehair.

BACKGROUND ART

In view of the unique composition of hair fibers and the numerouschanges that occur in styles and fashion, both the waving of hair andthe dyeing of hair have long been of particular interest. In particular,hair color alteration by dyeing while permanent waving hair forlong-lasting style retention have long been sought by many individuals.However, due to the composition of hair fiber, either the color or curlsare not retained as long as desired and the simultaneous permanentwaving and dyeing of hair fibers has not yet been achieved by anycommercially available product.

In order to best understand the reasons for the inability of the hairfiber to retain curls for substantially long time periods or to besimultaneously permanently waved and colored, it is important tounderstand that hair is composed of a unique protein material called"keratin" and which is distinguished by the fact that it contains a verysignificant amount of an amino acid (cystine) which contains the elementsulfur in addition to the elements nitrogen, oxygen, carbon andhydrogen. In the natural synthesis of hair, the element sulfurcovalently links intra or inter polypeptide chains (K) through twosulfur atoms (S-S) to give keratin protein (K-S-S-K). Only by chemicalaction can this covalent linkage be broken.

In this regard, many prior art compositions have been developed for the"cold permanent waving" of hair. Typically, these prior art systemstreat the hair with a reducing agent which breaks the disulfide(cystine) linkage in the hair. This chemical process typically followsthat after the hair is wound around a curling rod.

In general, permanent hair waving is usually carried out by subjectingthe hair to reagents containing a free--thiol group e.g., --SH. Thesematerials are also called mercaptans. In this treatment, the hairusually is either wrapped on the rods with water or the lotioncontaining the thiol, and then saturated with thiol lotion. The thiolwaving agent acts to break the disulfide bonds within the hair fiberforming thiol groups in the hair protein and disulfide bonds between twothiol waving agent molecules. The chemistry involved in the reaction ofthe mercaptan with the cystine disulfide bonds in the hair fiber isillustrated by the following chemical equations:

    KSSK+2RSH⃡2KSH+RSSR

    KSSK+RSH⃡KSSR+KSH

When a sufficient number of hair disulfide bonds have been broken, thehair is realigned to pair previously unpaired hair protein thiol groupsopposite each other. At this point, the hair is rinsed, removing theunreacted thiol waving agent and any water soluble disulfide reactionproducts formed from it. Then, the hair is saturated with an oxidizingagent, or neutralizer, such as hydrogen peroxide or bromate salt, toreform disulfide bonds between the newly paired hair protein thiols,thereby giving the hair a new configuration or wave, or adding curl tothe hair. By rebonding the sites of the reduced keratin in their newcurled configuration, a permanent set which is impervious to water isestablished.

Much of the rebonding of the reduced sites is accomplished by the actionof the chemical oxidizing agent, typically hydrogen peroxide, and can beillustrated by the following chemical reaction:

    2 KSH+H.sub.2 O.sub.2 →KSK+2H.sub.2 O

In the art of permanent waving, there is much trial and error, with thehair being over-processed, in some instances. The characteristics ofover-processing are raspy feel to the hair or a bleaching of the naturalunderlying color. Structural evaluation of the hair fiber by physicaland chemical analyses usually reveals that the structural integrity ofthe hair is lessened, which is evidenced by either an increase in theamount of cysteine and cystic acid; a lessening of the cystine contentrelative to the hair not so processed; or loss of tensile properties.

Some detrimental effect to hair fiber is unavoidable, as the process ofpermanent waving involves controlled bond scission of the disulfidelinkages within the keratin proteins. The recovery of these disulfidesis the determining factor for the tightness of the curls and overalltensile strength.

One problem typically encountered with the use of mercaptan reducingagents for the permanent waving of hair is that one lotion strength isneeded for virgin hair, while a different lotion strength is needed fordamaged or hair that had been previously chemically processed and,hence, difficult to wave. This problem is further compounded when thereis a mixture of both damaged as well as normal hair fibers on a head ofhair to be permanently waved. In particular, with either oxidatively ordeposit colored dyed hair, the subsequent application of mercaptanreducing agents causes a discoloring of the imparted dye in the hairfiber, thereby leaving the hair with an undesired or different shadethan had previously existed before the process.

Another problem typically found in the prior art occurs when anindividual wishes to dye hair which had been permanently waved. In thesecircumstances, the dye uptake will usually be uneven from the root tothe tip of the hair fibers due to the structural alteration caused tothe hair fiber by the permanent wave process.

In practice, this problem is often circumvented by waiting for the hairto "heal", by allowing for a substantial time interval in which aerialoxidation reseals the excessively damaged areas, thereby providing hairfibers which are more amenable to dye uptake in a level manner.

Although the consumer has long sought to have a composition and processwhich would enable both color and permanent waving to be achievedsimultaneously, no prior art system has been able to provide aneffective or reliable composition which would enable simultaneous dyeingand permanent waving of hair fibers. In fact, even though this need hasexisted in the art for decades, no successful commercial product hasbeen attained which satisfies the consumers' need.

One of the difficulties encountered in providing a prior art compositionwhich will achieve this simultaneous dyeing and permanent waving of hairfibers is due to the chemical nature of typical prior art dyestuffs. Ingeneral, oxidative dyestuffs are irreversibly altered in their colorupon contacting sulfurous materials, such as found in the permanent wavecompositions. Consequently, oxidative dyestuffs cannot be successfullyemployed with permanent waving compositions.

Alternatively, semi-permanent dyestuffs may be employed and have beenused to provide a temporary dyeing of the hair. However, such dyestuffstend to be removed from the hair upon washing and rubbing, or by theincreased porosity of hair resulting from chemical processing.Consequently, their incorporation into a permanent waving process doesnot provide the desired consumer result, since they are incapable ofproviding the permanent hair coloring effect desired by the consumer.

A further problem found with oxidatives or direct dyes is the fact thatthese materials are typically irritants or sensitizers of human skin.Consequently, these dyes should be employed either by skilledtechnicians or home users who are extremely careful to apply the dyesexplicitly in accordance with included directions.

Although numerous attempts have been made in the prior art to provide acombined permanent waving and hair dye product, no prior art product hasbeen successful in achieving a universally applicable or a commerciallyacceptable product.

Representative prior art attempts to meet the commercial demand arefound in various prior art patents. Those patent includes U.S. Pat. No.4,630,621, wherein a common oxidative dyestuff is added to theneutralizing composition for subsequent application to the hair afterthe hair has been treated with a permanent wave reducing solution.However, as discussed above, such oxidated dyestuffs must be usedcarefully by skilled technicians or individuals who are extremelycautious and careful with the dyes, due to the irritation that mayresult on the skin of the user.

In U.S. Pat. No. 4,781,724, a process is disclosed for simultaneouslydyeing and permanently waving white and gray hair. Although this patentteaches the incorporation of specific dyestuffs in the permanent wavereducing solution, the dyes taught herein are specifically limited touse on white and gray hair only. In addition, as will be detailed beloW,the operative pH range of the composition incorporating the dyestuffs issubstantially greater than the operative pH range of the presentinvention.

Other prior art patents, such as U.S. Pat. No. 3,299,682, U.K. Patent1,077,758 and U.S. Pat. No. 4,844,712 teach the use of variousdyestuffs. However, these patents do not provide any teaching ofcombining the dye with a permanent wave composition for achievingsimultaneous hair dyeing and permanent waving.

Furthermore, these prior art patents do not, in any way, teach orsuggest a permanent waving composition which comprises a pH rangingbetween 3.0 and 4.5. In fact, any of these prior art references whichdiscuss permanent waving specifically teach away from employing apermanent wave at this particular pH range and, instead, teachcompositions wherein the pH is 6.0 or greater.

Therefore, it is a principal object of the present invention to providea permanent waving composition which is capable of providingsubstantially tighter curls and longer lasting curls than previouslyattained in prior art systems.

Another object of the present invention is to provide a permanent wavingcomposition having the characteristic features described above which isalso capable of simultaneously dyeing the hair as an integral part ofthe permanent waving process, when desired by the consumer.

Another object of the present invention is to provide a permanent wavingcomposition and process for application thereof having thecharacteristic features described above which is capable of providingoptimum results at a pH level previously found unsuitable for permanentwaving of hair.

Other and more specific objects will in part be obvious and will in partappear hereinafter.

DISCLOSURE OF THE INVENTION

By employing the present invention, prior art difficulties and drawbackshave been eliminated and tighter, more durable permanent waving resultsare achieved as well as the ability to simultaneously color andpermanently wave the hair. It has been found that the prior artinabilities are completely eliminated by incorporating fluoroscein baseddyestuffs in a permanent wave composition comprising a mercaptanselected from the group consisting of an ester of either thioglycolicacid, thiolactic acid, or the amide of 2-aminoethanethiol. Furthermore,the resulting composition is maintained at a pH of between about 2.5 and4.5.

Depending upon the fluoroscein based dyestuff employed, the hair can besimultaneously permanently waved, while also being dyed. If the actualdyeing of the hair is not desired, the fluoroscein based dyestuff caneither be colorless or may employ a complimentary color, which wouldhighlight the hair.

Regardless of whether actual coloring is imparted to the hair fibers, ithas been found that the combination of a fluoroscein based dyestuff Withthe particular permanent waved composition, when maintained at a pH ofbetween about 2.5 and 4.5, provides heretofore unattainable results. Inparticular, the hair is permanently waved with substantially improvedcurl configuration, while also providing curls which are retained forsubstantially longer time periods than ever previously achieved.

By employing the present invention, it has been found that the hair ispermanently waved in a tight curl and, when desired, is also colored ina level, uniform and controlled fashion. It is believed that thefluoroscein based dyestuff acts synergistically in combination with thepermanent wave solution to promote curl impartation, resulting insubstantially improved results than ever previously attained.Furthermore, the permanent wave composition of this invention operatesat a pH of between about 2.5 and 4.5, a pH range which has typicallybeen incapable of providing acceptable results.

In developing the present invention, it has been found that thefluoroscein based dyestuff should comprise only dyestuffs which havebeen approved by the Food and Drug Administration. Consequently, all ofthe dyestuffs employed in the present invention comprise either F,D andC colors (suitable for foods, drugs, and cosmetics) or D and C colors(suitable for drugs and cosmetics). In addition to employing afluoroscein based dye, it is also required that the permanent wavecomposition comprise an ester of either thioglycolic acid, thiolacticacid, or the amide of 2-aminoethanethiol. It has been found that onlythese mercaptans in combination with a fluoroscein based dyestuffprovides the synergistic interaction herein described.

It has also been discovered that all of the suitable mercaptans inaccordance with this invention cause the fluoroscein based dyestuff tobecome discolored or colorless when intermixed therewith. In fact, thisphenomenon has been found to represent a characteristic requisite for acomposition that is capable of concurrently permanently waving andcoloring the hair.

In the preferred composition, the mercaptan comprises an ester ofthioglycolic acid with the ester being derived from one selected fromthe group consisting of glycerin, glyercol and glycosyl. In addition, ithas been found that the concentration of the fluoroscein based dyestuffshould range between 0.0000001 and 8.0% by weight of the totalcomposition, while the ester of the thioglycolic acid preferablycomprises a concentration ranging between 0.0001 and 30% by weight ofthe total composition.

The invention accordingly comprises a composition possessing thefeatures, proportions, and the relation of constituents, as well as theseveral steps and the relation of one or more of such steps with respectto each of the other, all as fully detailed herein, with the scope ofthe invention being indicated in the claims.

BEST MODE FOR CARRYING OUT THE INVENTION

In order to demonstrate the unique capabilities of the presentinvention, the following examples are provided, detailing variousaspects of this invention. These examples are intended as a teaching ofthe best mode for carrying out the present invention and are notintended to limit, in any manner, the breadth of this discovery.

By employing the compositions of this invention, substantially improvedcurl retention and hair strength are attained. In order to show thesubstantial enhancements provided by the present invention, a pluralityof comparative tests were conducted on hair permanently waved with thedifferent compositions formulated in accordance with the presentinvention. The results attained were compared to standard permanent wavecompositions, in order to demonstrate the efficacy of the presentinvention. In order to provide a useful and instructive comparativeanalysis, various test mixtures were prepared and applied to the hair asdetailed below. In Table I, the permanent wave composition employed inthe test mixtures are detailed, while Table II provides the compositionsemployed for the fluoroscein-based dyes and one triphenylmethane baseddye.

For purposes of clarity and explanation, the dyes are deatiled using thedesignations adopted by the Cosmetic, Toiletry, and FragranceAssociation (CTFA), and detailed in the CTFA Cosmetic IngredientDictionary, 4th Edition, Published 1991. In addition, the color indexnumbers for each specifid dye is also provided. In using the designationF,D & C or D & C, it is understood that the designated colors are to becertified according to the United States Certification Regulations.

                  TABLE I                                                         ______________________________________                                        Permanent Wave Compositions                                                   ______________________________________                                        Part A  Glycerine monothioglycolate 70%                                                                     32.5%                                                   in glycerine                                                          Part B  De-ionized water      98.44%                                                  Ammonium Chloride     1.50%                                                   Preservative          0.06%                                           Part C  Glycerin-thiolactic acid ester                                                                      32.5%                                                   (in 25% - glycerin)                                                   Part D  De-ionized water      88.5%                                                   Ammonium chloride     1.5%                                                    Animal protein, cocohydrolyzed                                                                      1.0%                                                    potassium salt                                                                Laureth ether         2.0%                                                    Fragrance             1.0%                                                    Polystyrene emulsifier                                                                              2.0%                                                    Ammonium hydroxide (28%) solution                                                                   4.0%                                            ______________________________________                                    

                  TABLE II                                                        ______________________________________                                        Part E    Propylene glycol   76.8%                                                      D&C Red No. 21 (CI 45380:2)                                                                      20.0%                                                      Monoethanolamine   3.2%                                             Part F    De-ionized water   79.8%                                                      D&C Red No. 22 (CI 45380)                                                                        20.0%                                                      Preservative       0.2%                                             Part G    De-ionized water   94.8%                                                      D&C Red No. 28 (CI 45410)                                                                        5.0%                                                       Preservative       0.2%                                             Part H    De-ionized water   79.8%                                                      D&C Blue No. 1 (CI 42090)                                                                        20.0%                                                      Preservative       0.2%                                             ______________________________________                                    

In Table III, each of the compositions tested is clearly presented as aseparate example, with the test results attained for each test samplealso provided for ease of comparison. In each of the examples providedin Table III, about one gram of medium brown hair was crimped at its endwith a metal staple and wetted with water. Next, the hair was wrappedabout a styling rod, secured with a rubber band and then saturated withthe particular composition mixture detailed in Table III.

The particular mixture was allowed to remain on the hair for abouttwenty minutes under a plastic wrapper, while being warmed with hotwater. At the end of the required time period, the hair was rinsed withrunning tap water and then saturated with a solution of 2% hydrogenperoxide stabilized with 0.2% phosphoric acid. This composition remainedon the hair for about five minutes and then the hair was thoroughlyrinsed with tap water.

The test results provided in Table III provide the degree of curl foundfor each test sample when the hair was dryed as well as afterforty-eight hour exposure to 90% humidity. For the purpose of thiscomparative study, the results provided represent the degree of curl(C), which is defined by the following equation: ##EQU1## where H is thetotal hair length d is the distance from the hair root to the firstcurl, and

n is the total number of curls.

In addition to comparing the curl resiliency for each of the testsamples, the strength of the resulting hair fibers was also determinedfor most of the test samples. These results are also provided in TableIII and were determined by using a tensile property determiningapparatus such as is available from the Instron Corporation,specifically their Model 20/20 Machine.

The results provided in Table III represent the amount of change intensile strength of the hair fiber as a comparison before and after thetreatment of the hair. In order to determine the tensile strength of theresulting hair fiber, the force needed to elongate the hair fiber by 10%before treatment is determined as well as the force needed to elongatedthe hair fiber by 10% after treatment. The test results provided inTable III represent the pre-treatment result minus the post-treatmentresult divided by the pre-treatment result. As is apparent from thisanalysis, values nearest to 1.00 indicate stronger relative tensileproperties.

                  TABLE III                                                       ______________________________________                                              Composition of                                                                             Degree of Curl    Instron                                  Ex-   Mixture                 After 48 Hrs                                                                             Force                                ample (Relative Parts)                                                                           pH    Dry  @ 90% Humidity                                                                           (S)                                  ______________________________________                                        1     Part A:Part D                                                                              9.2   1.00 1.07       1.00                                 2     Part A:Part B                                                                              4.0   1.40 1.53       1.03                                 3     Part A:Part B:                                                                             4.7   0.98 1.03       1.05                                       0.01 Part E                                                             4     Part A:Part B:                                                                             4.7   1.00 1.03       1.07                                       0.01 Part F                                                             5     Part A:Part B:                                                                             3.2   0.98 1.03       1.04                                       0.005 Part G                                                            6     Part A:Part B:                                                                             3.7   0.96 0.99       --                                         0.01 Part H                                                             7     Part B:Part C:                                                                             4.8   1.60            --                                         0.01 Part E                                                             8     Part B:Part C:                                                                             3.2   1.73            --                                         0.01 Part F                                                             9     Part B:Part C:                                                                             3.6   1.73            --                                         0.005 Part G                                                            10    Part A:Part B:                                                                             4.0   1.40 1.50       --                                         0.000001 CI                                                                   Basic Violet 10**                                                       11    Part A:Part B:                                                                             3.2   1.33 1.56       --                                         0.001 Basic Violet                                                            10 then, 20 vol.                                                              peroxide:CI                                                                   Acid Violet 43**                                                        12    Part A:Part B:                                                                             4.4   1.13 1.37       --                                         0.5% Merquat S*                                                         13    Part A:Part B:                                                                             4.4   1.43 1.41       --                                         1.0% Merquat S*                                                         ______________________________________                                         *Merquat S is the trade name for a quarternary amine component produced b     Merck, Inc.                                                                   **Colour Index number of dyestuff                                        

A review of the test results provided in Table III clearly demonstratesthat the inclusion of a fluoroscein-based dye in the permanent wavecomposition substantially improves the curl retention characteristics ofthe resulting permanent waved hair, as well as improving the structuralintegrity of the hair over hair reduced at an alkaline pH. Inparticular, where Xanthene and anthraquinone dyes were employed in therelaxing solution, the structural integrity of the resulting hair wasnot enhanced, as was provided by the fluoroscein-based dye stuffs.

In Table IV, examples of the range of colors attainable by employing thepresent invention are provided, along with the resistance to colorchange attained by the composition of this invention after repeatedshampooing or exposure to sunlight. Table IV clearly shows the increaseddurability of the dye when incorporated into the relaxing solution ofthe present invention as opposed to prior art conventional methods.

In Table IV, the hair samples were prepared and permanent waved asdetailed above in reference to Table III. The information provided inTable IV represents the chromicity values, L, A, and B for the same hairsample before and after seven shampoo, rinse and dry cycles, as well asafter exposure to ten hours of simulated sunlight. Except where noted,medium brown hair was used. All of the measurements were taken employinga Spectrogard II system available from Pacific Instruments.

                                      TABLE IV                                    __________________________________________________________________________    Composition of     Chromicity Values:  .sub.-- L,  .sub.-- A,  .sub.-- B           Mixture             After  After 10 Hrs                                  Example                                                                            (Relative Parts)                                                                       Color                                                                              Initial                                                                             Shampooing                                                                           Shampooing                                    __________________________________________________________________________    14   Part A:Part B:                                                                         Light                                                                              L = 21.84                                                                           L = 21.45                                                                            L = 20.36                                          0.01 part F                                                                            Auburn                                                                             a = 11.66                                                                           a = 11.62                                                                            a = 14.28                                                        b = 10.07                                                                           b = 10.39                                                                            b = 9.31                                      15   Part A:Part B:                                                                         Auburn                                                                             L = 21.25                                                                           L = 20.99                                                                            L = 21.48                                          0.01 Part E   a = 12.08                                                                           a = 11.49                                                                            a = 12.69                                                        b = 9.65                                                                            b = 9.43                                                                             b = 9.49                                      16   Part A:Part B:                                                                         Dark L = 21.18                                                                           L = 20.64                                                                            L = 22.28                                          0.01 Part G                                                                            Auburn                                                                             a = 9.11                                                                            a = 9.68                                                                             a = 8.70                                                         b =  6.71                                                                           b = 7.93                                                                             b = 8.59                                      17   Part A:Part B:                                                                         Blue/                                                                              L = 15.33                                                                           L = 15.75                                                                            L = 16.28                                          0.01 Part D                                                                            Brown                                                                              a = 2.15                                                                            a = 2.21                                                                             a = 2.38                                                         b = 3.31                                                                            b = 3.29                                                                             b = 3.23                                      18   Part A:Part B:                                                                         Blue/                                                                              L = 39.90                                                                           L = 41.55                                                                            L = 43.15                                          0.01 part D on                                                                         Grey a = -2.00                                                                           a = -3.24                                                                            a = -3.65                                          blended grey hair                                                                           b = 0.32                                                                            b = 0.31                                                                             b = 0.30                                      19   Part A:Part B:                                                                         Pink L = 41.70                                                                           L = 41.27                                                                            L = 41.65                                          0.01 Part F on                                                                              a = 49.44                                                                           a = 49.25                                                                            a = 49.33                                          White Hair    b = 27.44                                                                           b = 27.05                                                                            b = 26.93                                     20   Part B: 0.01                                                                           Light                                                                              L = 55.00                                                                           L = 78.26                                                                            L = 56.92                                          on White Hair                                                                          Pink a = 20.76                                                                           a = 8.72                                                                             a = 13.70                                                        b = 3.14                                                                            b = 6.55                                                                             b = 5.36                                      __________________________________________________________________________     Chromicity values of .sub.-- L = total reflectance of 0 = black, 100 =        white; a = (+) for red; (-) for green; -b = (+) yellow, (-) for blue as       determined by the average of triplicate measurements performed on a           Spectrogard II system available from Pacific Instruments.                

It will thus be seen that the objects set forth above, among those madeapparent from the preceding description are efficiently attained and,since certain changes may be made in the composition detailed herein, aswell as in carrying out the above process without departing from thescope of the invention, it is intended that all matter contained in theabove description shall be interpreted as illustrative and not in alimiting sense.

It is to be understood that the following claims are intended tocoverall of the generic and specific features of the invention hereindescribed and all statements of the scope of the invention which, as amatter of language, might be said to fall therebetween.

Particularly, it is to be understood that in said claims, ingredients orcompounds recited in the singular are intended to include compatiblemixtures of such ingredients wherever the sense permits.

Having described our invention, what we claim as new and desire tosecure by Letters Patent is:
 1. A composition for simultaneouslycoloring and permanently waving hair, said composition comprisingA. apermanent waving composition selected from the group consisting of anester of thioglycolic acid, an ester of thiolactic acid and an amide of2-aminothiol, and B. a fluorescein-based dye,The entire compositionhaving a pH ranging between about 2.5 and 4.5 whereby hair ispermanently waved having a substantially improved curl retention.
 2. Thecomposition defined in claim 1, wherein said fluorescein-based dye isfurther defined as imparting a particularly desired color to the hair.3. The composition defined in claim 1, wherein said fluorescein-baseddye is further defined as being colorless, thereby preventing any haircolor change, while enabling the hair to be permanently waved with asubstantially improved curl configuration.
 4. The composition defined inclaim 1, wherein said fluorescein-based dye is further defined ascomprising between about 1×10 -7 and 8% by weight of the totalcomposition.
 5. The composition defined in claim 4, wherein saidfluorescein-based dye is further defined as comprising a dye certifiedby the Food and Drug Administration and bearing the designation of F,D &C or D & C.
 6. The composition defined in claim 4, wherein saidfluorescein-based dye is further defined as comprising at least oneselected from the group consisting of D & C Red No. 21, D & C Red No.22, and D & C Red No.
 28. 7. The composition defined in claim 1, whereinsaid permanent wave composition is further defined as comprising anester of thioglycolic acid with the ester being derived from oneselected from the group consisting of glycerin, glycerol and glycosyl.8. The composition defined in claim 7, wherein said permanent wavecomposition is further defined as comprising a concentration rangingbetween about 1×10 -4 and 30% by weight of the total composition.
 9. Acomposition for simultaneously coloring and permanently waving hair,said composition comprisingA. between about 1×10⁻⁴ and 30% by weight ofthe total composition of a permanent waving composition incorporating anester of thioglycolic acid, with said ester being derived from oneselected from the roup consisting of glycerin, glycerol and glycosyl; B.between about 1×10⁻⁷ and 8% by weight of the total composition of afluorescein-based dye selected from the group consisting of D & C RedNo. 21, D & C Red No. 22, and D & C Red No. 28; and C. the balance ofthe composition being substantially formed by water with the resultingpH ranging between about 2.5 and 4.5.
 10. A composition forsimultaneously coloring and permanently waving hair, said compositioncomprisingA. between about 1×10⁻⁴ and 3% by weight of a permanent wavingcomposition selected from the group consisting of an ester ofthioglycolic acid, an ester of thiolactic acid, and an amide of2-aminothiol and; B. between about 1×10⁻⁷ and 8% by weight of afluorescein-based dye;the entire composition having a pH ranging betweenabout 2.5 and 4.5, whereby a composition is attained which is capable ofpermanently waving hair with a substantially improved curl retentionquality.